title: The extent of non-Born-Oppenheimer coupling in the reaction of Cl(2P) with para-H2.
abstract: Elementary triatomic reactions offer a compelling test of our understanding of the extent of electron-nuclear coupling in chemical reactions, which is neglected in the widely applied Born-Oppenheimer (BO) approximation. The BO approximation predicts that in reactions between chlorine (Cl) atoms and molecular hydrogen, the excited spin-orbit state (Cl*) should not participate to a notable extent. We report molecular beam experiments, based on hydrogen-atom Rydberg tagging detection, that reveal only a minor role of Cl*. These results are in excellent agreement with fully quantum-reactive scattering calculations based on two sets of ab initio potential energy surfaces. This study resolves a previous disagreement between theory and experiment and confirms our ability to simulate accurately chemical reactions on multiple potential energy surfaces.
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, People's Republic of China.
authors.forename: Xingan
authors.initials: X
authors.lastname: Wang
authors.forename: Wenrui
authors.initials: W
authors.lastname: Dong
authors.forename: Chunlei
authors.initials: C
authors.lastname: Xiao
authors.forename: Li
authors.initials: L
authors.lastname: Che
authors.forename: Zefeng
authors.initials: Z
authors.lastname: Ren
authors.forename: Dongxu
authors.initials: D
authors.lastname: Dai
authors.forename: Xiuyan
authors.initials: X
authors.lastname: Wang
authors.forename: Piergiorgio
authors.initials: P
authors.lastname: Casavecchia
authors.forename: Xueming
authors.initials: X
authors.lastname: Yang
authors.forename: Bin
authors.initials: B
authors.lastname: Jiang
authors.forename: Daiqian
authors.initials: D
authors.lastname: Xie
authors.forename: Zhigang
authors.initials: Z
authors.lastname: Sun
authors.forename: Soo-Y
authors.initials: SY
authors.lastname: Lee
authors.forename: Dong H
authors.initials: DH
authors.lastname: Zhang
authors.forename: Hans-Joachim
authors.initials: HJ
authors.lastname: Werner
authors.forename: Millard H
authors.initials: MH
authors.lastname: Alexander